Manufacture of improved fibrous materials and the materials thus obtained



in theisaid solutions. derivedirom sulfonic acid amides containing a:saturated aliphatic hydrocarbon radical of at least 8 carbon atoms.sulfamides are readily soluble in the alkaline Patented May 24, 1949UNITED STATES iFllCE 'MANUFACTURE OF IMPROVED FIBROUS IVIATERIl-KLS ANDTI-IE'MATERIALS THUS OBTAINED Ludwig Orthner, Gerhard Balle, and HeinzScliil'd, Frankfort-on-the-Main,Max-Otto Scliiirmann, Dorma'gen,"andKarl Brodersen and Matthias 'Quaedvlieg, -Dessau, Germany; vested in--the Attorney General. of the United' 'states .No Drawing. iApplicationFebruary 2.6, 1941,.Serial'N0."38.0,6?'2. In Germany February.21,.1940

- Section 1, PubliczLaw 690, -August-8f194'6 5 Patent: expires February21,1960

(Cl. v1061(i5) '7 Claims. ,1

The *present :invention ."relates to a process of manufacturing'artificial tfibrous materials and to the materials thus obtained. It isan object of the invention toiprepare fibers having an agreeable, softhandle. :Itiswa-iurther objectof the invention'to impart tothefibersa-soft and elastic feel stable .to' thenisualwashing operations. The

:invention especially relates to the process of improving artificialfibrous materials which com- :prises incorporating in the aqueousspinning solution alkali compounds of sulfonic acid amides containing asaturated aliphatic hydrocarbon radical of at least Bcarbonatoms. In themanu- .1 facture of improved artificial filaments from aqueoussolutions, e. g. cellulose spinning solutions, such as viscose-orcuprammonlum solutions .of cellulose or protein spinning solutions,

alkali compounds'are added which are soluble The alkali compounds are Ingeneral the said spinningsolutions; only in the cases the molecuilarweight of the sulfamide is extremely high,

there is not'obtained :a clear solution in alkaline fluids, but asuspension or emulsion is formed which may be stabilized bythe: additionof the usual dispersing agents "and which is likewise suitable for theipresent process. Furthermore, mixtures :of sulfamides may be used,forinstance mixtures of compounds of high molecular weight and ofcompounds of lower'molecular weight. The aqueous spinning solutionscontaining alkali compounds of sulfonic ':acid amides having .asaturated aliphatic hydrocarbon radical of at least '8' carbon atoms arespun in the usual way into a known spinning'ba'th containing forinstance sulfuric acid and Glauberistsalt.

-Su1famides of high molecular weight and. their alkali compounds maybeipreparedin different ways: by transformation of alcohols of highmolecular weight into halogen compounds, reaction of theha'logencompounds with sodium 'sulfite to form-sulfonic acids andtransformationof said acids or their alkali metal saltsinto the correspondingsulfo'chlor-i'des or sulfobromides, for instance withphosphoruspentachloride, and transformation of the -=sulfochlorides withammanufacture r of artificial 'tfibers 'suitably :by the .sulfonamides.

:simultaneous action :of chlorine xdioxide on saturated aliphatic.hydrocarbons having at least 8- carbon atoms with ammonia, .or amineslor:hydroayamines. lBythe :selection ethylamine, butylamine,-.d"ode'cylamine, cyclohexylamine, aniline, furthermore: hydroxyamines,

such as aethanolamine,;.propanolamine, .butanolamine or oxethylaniline,into z-the corresponding At 'this synthesis rthere may likewise :bestarted from alcohols of high :molecular weight as they are,for;instance, cbtainedbythe reduction of fats and,oils ofltatty-acids.or the like.

'Sulfamides of hi ghimolecular weight are'ob- .tained in atechnically;especially-simple manner :by the reaction of sulfochloridesformed by the and :sulfur of .the hydrocarbons -'or hydrocarbon mixturesserving .as starting :'material, the effect attainable-with'th'esulfa-mides-may'sbe variedtola large extent.

There may berstar-ted from hydrocarbons or from "mixtures ofhydrocarbons which are obwta-ined tby iractionating.petroleum orfromprodducts whichare ohtained 'by the hydrogenation of carbon orthereduction ofecarbon monoxide. I'Ihese technical productsmaybe freedfrom any unsaturated portions which may be ,present, by .zihydrogenationor refining. rmayzbe reacted with chlorine and sulfur dioxide Thehydrocarbons with exposure ato aultraviolet .rays. .The hydro- :carbons'may be used in- BXOESS,';S0 that only a :part is 1transformed:..intorproducts containing chlorine,'sulfuriandlxoxygen. "The excess of the:hy'drocarbon may she separatedimmediately or after the 'rea'ction withammonia or amines.

Sulfamides which are kl-useful .JfOr n'the rpresent process may alsobesobtaine'd for'instance as'follows: carboxylic acids haVing analiphatic hydrocarbon 'radical of at least 8:.carbon atoms are caused toreact --..with sulfamides containing amino groups, for instanceby thecondensation "of lauric acid with *meta aminobenzeneesulfamide 0rbeta-aminoethane-sulfamide.

The sulfamides herein described may be incorporated in the spinningsolutions zused for the -addition of :an alkalinesolutionnf thezsuliamide to :the :spinning ssolution,:- foriinstance ;a viscosesolution 1 or the ;solution :of sccel-lulose :in copper primarymasesf has methylamine, 1-60 .oxiderzarld ammonia. nuringssa-id:operationthesolubility or distributability in alkali may be enhanced by thesimultaneous use of dispersing agents, such as alcohol-sulfonates,condensation products of carboxylic acids of high molecular weight andamino-sulfonic acids or hydroxy-sulfonic acids or amino-carboxylic acidsor hydroxycarboxylic acids, aromatic sulfonic acids, for instancealkyl-naphthalenesulfoni acids, condensation products fromethylene-oxide and alcohols of high molecular weight, carboxylic acidsof high molecular weight, alkylphenols, alkylcyclohexanols and others.The sulfamide may be added to the spinning solution in any desired phaseof its preparation. The alkaline solutions of the sulfamides may also beincorporated without any diificulty to the spinning solutions for caseinfibers. The spinning solutions to which the sulfamide has been added areworked up in the usual manner in the usual devices. During the formationor the after-treatment of the threads in the usual acid precipitatingbath the sulfamide is separated from its alkaline solution and finelyand uniformly subdivided in the thread. During the preparation of caseinfibers while simultaneously using sulfamides a reaction of the sulfamidewith the formaldehyde moreover probably occurs during the usualhardening operation; a good fixing in the fiber of the substance addedis thus attained.

The artificial fibers thus obtained are distinguished by a soft andelastic feel. Owing to the insolubility of the sulfamides in alkalicarbonates the incorporated substance imparting softness is not removedfrom the fiber by the usual washing operations when washing liquidscontaining sodium carbonate are used. According to the present processartificial fibers are obtained which contain the softening agent notonly at the surface; on the contrary, the product imparting softness isuniformly subdivided also in the interior of the fiber. The goodsubdivision is attained by the fact that the product is present in thespinning solution in the form of a molecular or colloidal solution. Ifthe fiber is formed in the acid spinning bath it is uniformlyprecipitated in an insoluble form. The softening effect produced is,therefore, more stable than in those cases where the fibers are treatedwith water-soluble softening agents which are absorbed by the fiber. Inthat case salts of amines of high molecular weight are frequently used.The free amines are, as is known, insoluble in alkaline spinningsolutions and can, therefore, not be incorporated in the same manner asthe alkali metal compounds of sulfamides. Furthermore, quaternaryammonium compounds of high molecular weight or other water solublebodies are used as softening agents. If the compounds Of said kind arealready used on spinning it is found that the effect produced is notvery resistant to washing operations owing to the solubility in water ofthe compounds.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight:

1. 4000 parts of a viscose solution containing about 5 per cent ofcellulose are mixed with a solution in 2N-caustic soda solution of asulfamide obtained by the simultaneous action of chlorine and sulfurdioxide on a benzine fraction mainly containing saturated aliphatichydrocarbons and boiling between 240 C. and 340 C. formed by reductionof carbon monoxide and a subsequent reaction of the aliphaticsulfochlorides formed with ammonia. The solution is spun in known mannerinto an acid precipitating bath. The fibers obtained are after-treatedin the usual manner and dried and are distinguished by an excellentsoftness and suppleness.

A similar effect is attained by using an aliphatic sulfamide prepared bythe simultaneous action of chlorine and sulfur dioxide on a paraffinefraction boiling between 340 C. and 380 C. and a subsequent reactionwith ammonia.

The viscose solutions may also be worked up by a process of spinning bystretching the filement.

2. kilograms of casein are caused to swell at 24 C. in 200 liters ofwater, a mixture of 23 liters of caustic soda solution of 35 per centstrength and 7'7 liters of water is added and the whole is then dilutedwith water so as to obtain 550-600 liters of a clear, alkaline caseinsolution. 5 kilograms of a mixture of sulfamides prepared by thesimultaneous action of chlorine and sulfur dioxide on a mixture ofparafiine wax formed during the benzine synthesis by the catalyticreduction of carbon monoxide and a subsequent reaction of thesulfochlorides obtained with ammonia is dissolved in 2N-caustic sodasolution and the solution is added to the spinning solution. After thesolution has been allowed to ripen in the usual manner it is spun intoan acid precipitating bath. The filament formed is then hardened in theknown manner with formaldehyde. The artificial fibers obtained aredistinguished by an agreeable and soft feel.

3. 46 parts of sulfamide (obtained by the simultaneous action ofchlorine and sulfur dioxide on a mixture of hydrogenated hydrocarbons bythe reduction of carbon monoxide and boiling between 240 C. and 340 C.and a subsequent reaction of the sulfochlorides formed with ammonia) arestirred with 9.5 parts of ZN-caustic soda solution, while adding 4.6parts of the product of the reaction between octadecyl alcohol and 10mol of ethylene oxide. The whole is diluted with about 300 parts of coldwater and stirred into 12,700 parts of a solution of 9 per cent strengthof cellulose in copper oxide and ammonia. The solution is then spun by aprocess of spinning by stretching the filament so as to obtainartificial silk. The skeins are Washed as usual with acid and Water,then agitated for 5 minutes in water heated to 65, centrifuged anddried. The artificia1 silk thus obtained has a soft feel even withoutthe usual after-treatment with softening agents.

4. 40 parts of a sulfamide (obtained by the simultaneous action ofchlorine and sulfur dioxide on a parafiine fraction mainly containingsaturated aliphatic hydrocarbons and boiling between 320 C. and 380 C.and a subsequent reaction of the aliphatic sulfochlorides formed withmethylamine) are dissolved in 2N-caustic soda solution. The solution isstirred into 4000 parts of a viscose solution containing about 6 percent of cellulose. The solution produced is spun in known manner into anacid precipitating bath. The fibers obtained are distinguished, afterhaving been Worked up in the usual manner and dried, by a soft andsupple feel.

A similar effect is attained by using an aliphatic sulfamide obtained bythe simultaneous action of chlorine and sulfur dioxide on the paraflinefraction named above and a subsequent reaction with aniline. The produceis suitably dissolved in lN-caustic soda solution.

5. 4000 parts of a viscose solution contain- ..ing about 6 per cent ofcellulose are mixed with a solution in 2N-caustic soda solution of 8parts of a sulfamide substantially containing 16 to 18 carbon atoms andobtained by the reaction of a mixture of cetyl alcohol and octadecylalcohol with thionyl chloride so as to obtain the correspondingchlorides, reaction of the chlorides with sodium sulfite so as to obtainthe corresponding sulfonic acid salts, transformation of the sulfonicacid salts with phosphorus pentachloride into the corresponding sulfonicacid chlorides and finally reaction of the sulfochlorides with ammoniato obtain the corresponding sulfamides. The solution is spun into anacid precipitating bath and worked up as usual. The fibers obtained havea very good softness and suppleness.

6. To 4000 parts of a viscose solution containing about 6 per cent ofcellulose there is added an alkaline casein solution prepared bydissolving 40 parts of casein in the corresponding quantity of alkalilye. To the solution thus produced there are added 6 parts of asulfamide obtained by the simultaneous action of chlorine and sulfurdioxide. on a benzine fraction containing saturated aliphatichydrocarbons and boiling between 230 C. and 320 C. and the subsequentreaction of the sulfochlorides formed with ammonia. For said purpose thesulfamide is dissolved in 2N-caustic sod-a solution, while adding 1 percent of an emulsifying agent, for instance the product of reaction ofoctadecyl alcohol and mol of ethylene oxide. The spinning solutionformed is worked up in the usual manner to obtain fibers which afterhaving been hardened with formaldehyde are distinguished by an agreeableand soft feel.

We claim:

1. The process of improving cellulose fibrous materials distinguished bya soft and agreeable feel without the usual treatment with softeningagents which comprises incorporating with the aqueous cellulose spinningsolution colloidal alkali compounds of a sulfonic acid amide obtained bythe simultaneous action of chlorine and sulfur dioxide on a mixture ofsaturated aliphatic hydrocarbons boiling from 240 C.-340 C. formed bythe reduction of carbon monoxide, and subsequent reaction with ammonia,said sulphonic acid amids being insoluble in alkali carbonates and beinguniformly subdivided in the interior of the fiber.

2. The process of improving cellulose fibrous materials distinguished bya soft and agreeable feel without the usual treatment with softeningagents which comprises incorporating with the aqueous cellulose spinningsolution colloidal alkali compounds of a sulfonic acid amide obtained bythe simultaneous action of chlorine and sulfur dioxide on a mixture ofsaturated aliphatic hydrocarbons boiling from 340 C.- 380 C. formed bythe reduction of carbon monoxide, and subsequent reaction with ammonia,said sulphonic acid amids being insoluble in alkali carbonates and beinguniformly subdivided in the interior of the fiber.

3. Cellulose fibrous materials distinguished by a soft and agreeablefeel without the usual treatment with softening agents and havinguniformly distributed therethrough a colloidal sulfonic acid amide beinginsoluble in alkali carbonates and obtained by the simultaneous actionof chlo- '6 rine and sulfur dioxide on a mixture of saturated. aliphatichydrocarbons boiling from 240 C.-340 C. formed by the reduction ofcarbon monoxide, and subsequent reaction with ammonia.

4. Cellulose fibrous materials distinguished by a soft and agreeablefeel without the usual treatment with softening agents and havinguniformly distributed therethrough a colloidal sulfonic acid amide beinginsoluble in alkali carbonates and obtained by the simultaneous actionof chlorine and sulfur dioxide on a mixture of saturated aliphatichydrocarbons boiling from 340 C.- 380 C. formed by the reduction ofcarbon monoxide, and subsequent reaction with ammonia.

5. The process of improving artificial fibrous materials distinguishedWith a soft and agreeable feel without the usual treatment withsoftening agents Which comprises incorporating with the aqueous spinningsolution colloidal alkali compounds of sulfonic acid amides obtained bythe simultaneous action of chlorine and sulfur dioxide upon saturatedaliphatic hydrocarbons having at least 8 carbon atoms and subsequentamidation with a substance selected from the class consisting of ammoniaand primary amines, said sulphonic acid amids being insoluble in alkalicarbonates and bein uniformly subdivided in the interior of the fiber.

6. Artificial fibrous materials distinguished by a soft and agreeablefeel without the usual treatment with softening agents and havinguniformly distributed therethrough colloidal sulfonic acid amides beinginsoluble in alkali carbonates and obtained by the simultaneous actionof chlorine and sulfur dioxide upon saturated aliphatic hydrocarbonshaving at least 8 carbon atoms and subsequent amidation with a substanceselected from the class consisting of ammonia and primary amines.

7. The process as defined in claim 1 wherein 46 parts by weight of thesulfonic acid amide are incorporated in 12,700 parts by weight of asolution of 9 per cent strength of cellulose in copper oxide andammonia.

LUDWIG ORTHNER. GERHARD BALLE.

HEINZ SCHILD. MAX-OTTO scHiiRMANN. KARL BRODERSEN. MATTHIAS QUAEDVLIEG.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,947,939 Hubert Feb. 20, 19342,002,613 Orthner et al May 28, 1935 2,047,066 Glietenberg July 7, 19362,069,804 Heckert Feb. 9, 1937 2,112,728 Morgenstern Mar. 29, 19382,142,934 Bruson Jan. 3, 1939 2,174,507 Tinker Sept. 26, 1939 2,197,800Henke Apr. 23, 1940 2,213,360 Calcott Sept. 3, 1940 2,225,960 Orthner etal. Dec. 24, 1940 2,300,589 Nelles Nov. 3, 1942 2,316,242 Hentrich Apr.13, 1943 2,335,592 Hill Nov. 30, 1943

